A spin-level addressable nitrogen-intercalated indanone-C 60 Derivatives and their preparation methods

Abstract

The application discloses a nitrogen-embedded indenone and C 60 Derivative and a preparation method thereof. The preparation adopts a double-cavity structure with an ion source cavity and a reaction cavity connected in series, and the preparation method comprises the following steps: taking the indenone and C 60 Derivative as a sublimation raw material, and using a nitrogen-containing ion beam current to bombard the sublimated indenone and C 60 Derivative, so as to realize ion implantation and directly form the nitrogen-embedded indenone and C 60 Derivative. Through modification of the indenone, zero-field splitting is introduced, spin transition of the embedded nitrogen atom is degenerate, and the nitrogen-embedded indenone derivative has good spin energy level addressability. The zero-field splitting parameters are respectively calibrated as |D| = 17.17 MHz and E = 0.39 MHz. The double difficulties of difficulty in synthesis of intrinsic nitrogen-embedded fullerene and invalid loss of intrinsic nitrogen-embedded fullerene caused by a chemical modification process are overcome.

Description

Technical Field

[0001] This invention belongs to the field of carbon-based spin quantum materials, specifically relating to a spin-addressable nitrogen-intercalated indanone-C 60 Derivatives and their preparation methods. Background Technology

[0002] Carbon-based spin quantum materials include endogenous fullerenes, diamond NV centers, graphene, and carbon nanotubes. Among these, endogenous fullerenes are compounds in which heteroatoms, ions, clusters, or molecules are embedded within a fullerene cage. This core-shell structure endogenous fullerenes possess unique chemical, physical, and magnetic properties. Nitrogen-intercalated fullerenes (N@C) are a prime example. 60 Because there is no charge transfer between the embedded nitrogen atom and the fullerene, and the carbon atoms in the fullerene have zero nuclear spin, and the uncommon van der Waals core-shell configuration of the carbon cage prevents its kinetic release or reaction with the external environment, N@C 60 With excellent coherence properties, N@C is considered a highly promising candidate material for qubits. However, unlike embedded atoms or molecules such as metal atoms, clusters, and inert gases, which can exist stably on their own, N@C... 60 Currently, N@C can only be synthesized via ion implantation, with a spin content typically around 0.01% in the reaction product and a yield often below 10%. The high difficulty in preparation and purification limits the development of N@C. 60 Applications.

[0003] Cage-based chemical modification of endohedral fullerenes is a necessary means to extend their properties and broaden their application range. For intrinsic N@C 60 As far as C is concerned, 60 The extremely high symmetry of nitrogen atoms means that the single-electron spin level structure cannot be fully utilized, thus often requiring the optimization of intrinsic N@C atoms. 60 Chemical modification of carbon cages can actively introduce zero-field splitting to achieve efficient qubit expansion and addressing. However, the chemical modification process also suffers from cumbersome steps and significant ineffective losses of intrinsically intercalated fullerenes. This severely restricts the development of nitrogen-intercalated fullerene technologies. Therefore, it is necessary to seek a new technical solution to achieve efficient modification of nitrogen-intercalated fullerenes. Summary of the Invention

[0004] For intrinsic N@C 60 To address the issues of unaddressable energy levels and the cumbersome steps and significant ineffective losses of intrinsically intercalated fullerenes in existing chemical modification processes, this invention provides a spin-addressable nitrogen-intercalated indanone-C 60 The derivative and its preparation method are based on indanone C 60 Preparation of derivatives containing nitrogen-intercalated indanone and C 60The method for preparing derivatives is simple and easy to implement, avoiding the ineffective losses caused by chemical modification processes to the endohedral fullerenes, and improving the preparation efficiency of endohedral fullerene derivatives.

[0005] The technical solution of the present invention is as follows:

[0006] This invention prepares spin-level addressable nitrogen-intercalated indanone and C 60 The derivative process employs a dual-cavity structure with an ion source cavity and a reaction cavity connected in series. The described spin-level addressable nitrogen-intercalated indanone C... 60 The method for preparing the derivative includes the following steps: using indanone-C 60 The derivative was used as a sublimation raw material, and the sublimated indanone was bombarded with a nitrogen-containing ion beam and C 60 The derivatives are then deposited onto the substrate surface at the cold end to form a thin film. After the reaction, the substrate with the deposited film is sonicated in a solution, filtered, and dried to obtain a spin-addressable nitrogen-intercalated indanone with C12O4. 60 derivative.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] A spin-level addressable nitrogen-intercalated indanone-C 60 The method for preparing the derivative includes the following steps:

[0009] S1, Add 500mg of indanone and C 60 The derivative powder raw material is placed in a crucible, and then the crucible is placed in a sublimation furnace. The substrate is placed at the cold end of the reaction, and the sublimation furnace is located inside the reaction chamber. The substrate is an 8μm copper foil substrate.

[0010] The aforementioned reaction chamber is a dual-chamber structure consisting of an ion source chamber and a reaction chamber connected in series, as detailed below:

[0011] The reaction chamber is a cube with a length of 620mm, a width of 520mm, and a height of 500mm; the ion source chamber is a cylinder with an inner diameter of 250mm and a height of 300mm; the circular bottom of the ion source chamber is connected to the side of the reaction chamber (i.e., the side with a width of 520mm and a height of 500mm), and the chambers are connected by an adjustable orifice plate with a diameter of 5mm-50mm; the pump unit is connected to the reaction chamber and is located away from the chamber where the ion source is located.

[0012] S2. A two-stage pump system consisting of a mechanical pump and a molecular pump is used to pump the gas pressure in the reaction chamber to 10. -3 Pa controls the sublimation furnace to heat up to 450℃ in 45 minutes and hold for 1 hour, while setting the cold end temperature to -10℃ to improve the product collection efficiency.

[0013] S3. When entering the heat preservation stage, introduce a gaseous precursor gas source with a purity of ≥99.99% and a purity of 10 sccm, and turn on the ionization switch of the magnetron sputtering ion source, set the ion source power, and convert the precursor gas source into a nitrogen-containing low-temperature plasma beam until the reaction ends.

[0014] S4. After the heat preservation stage, indanone and C are controlled by PID. 60 The sublimation rate of the derivative is The temperature is 500℃-650℃ until the indanone C in the crucible is obtained. 60 The derivatives were completely sublimated, and the entire process was controlled within 6 hours. During the reaction, the copper foil at the cold end of the reaction chamber was wound up at a rate of 0.005 r / min to collect the reaction products.

[0015] S5. After the reaction is complete, the sublimation furnace is stopped from heating and allowed to cool naturally to room temperature. The pump group is then turned off to restore the gas pressure in the reaction chamber to the normal pressure. The copper foil substrate is then removed and placed in a toluene solution. After sonication, filtration, and drying, a spin-addressable nitrogen-intercalated indanone and C2 are obtained. 60 derivative.

[0016] In this invention:

[0017] The spin-level addressable nitrogen-intercalated indanone and C described in S1 60 The derivatives are stable at high temperatures, and their structure is not destroyed during the reaction.

[0018] The tandem dual-chamber structure described in S1 can create a pressure gradient distribution during the reaction process. After introducing a 10 sccm gaseous precursor gas source, the gas pressure in the reaction chamber is 10. -2 The gas pressure in the magnetron sputtering ion source cavity is 10 Pa. -1 pa.

[0019] The setting of the cold end temperature to -10℃ as described in S2 to improve the product collection efficiency means that if the cold end (collection end) temperature is room temperature, then its temperature is the same as the inner wall of the chamber, so the product will not be concentrated on the copper foil, but will be distributed throughout the inner wall of the chamber; setting the cold end temperature to -10℃ is significantly lower than the inner wall of the reaction chamber, so the product will tend to be deposited on the copper foil on the cold end.

[0020] The low-temperature plasma beam described in S3 bombards the sublimated indanone and C in the reaction chamber. 60 Derivatives, forming nitrogen-intercalated indanone and C 60 derivative.

[0021] The gaseous precursor gas source mentioned in S3 is nitrogen or ammonia, or a mixture of nitrogen, nitric oxide, nitrogen dioxide, and ammonia; the low-temperature plasma beam bombards the sublimated indanone and C in the reaction chamber. 60 Derivatives, forming spin-addressable nitrogen-intercalated indanone and C 60 derivative.

[0022] This invention also relates to a spin-level addressable nitrogen-intercalated indanone-C 60 Derivatives, based on the aforementioned spin-level addressable nitrogen-intercalated indanone and C 60 The derivative was prepared using a method characterized by N@C modification via indanone. 60 The symmetry breaking leads to zero-field splitting, which degenerates the electron spin transitions of the embedded nitrogen atoms and gives them good spin level addressability. The zero-field splitting parameters are calibrated as |D| = 17.17 MHz and E = 0.39 MHz, respectively.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. A spin-level addressable nitrogen-intercalated indanone-C 60 Compared with the current traditional method of modifying endogenous fullerenes, which involves first synthesizing intrinsic endogenous fullerenes and then performing chemical modifications, the method of preparing derivatives directly using fullerene derivatives with pre-existing modified structures avoids the ineffective loss of intrinsic endogenous fullerenes during chemical modifications, significantly improves the modification efficiency of endogenous fullerenes, and opens up new avenues for the efficient modification of other endogenous fullerenes.

[0025] 2. A spin-level addressable nitrogen-intercalated indanone-C1000 ionosphere prepared by this invention 60 The derivatives have a relatively simple composition, avoiding complex reactions and byproduct generation during chemical modification, which can effectively improve separation and purification efficiency and is more conducive to their application in the field of quantum information.

[0026] 3. With intrinsic N@C 60 In comparison, the nitrogen-intercalated indanone-C described in this invention 60 The derivative has addressable spin energy levels and is a novel carbon-based spin quantum material.

[0027] 4. A spin-level addressable nitrogen-intercalated indanone-C1000 ionosphere according to the present invention 60In one method for preparing derivatives, a dual-cavity structure, where the ion source cavity and reaction cavity are connected in series, reconciles the conflict between the high vacuum atmosphere required for the embedded reaction process and the low vacuum environment needed for stable operation of the magnetron sputtering ion source. The series dual-cavity structure, connected by a perforated plate, creates a pressure gradient distribution during the reaction: the high vacuum in the reaction cavity can facilitate the production of indanone-C... 60 The sublimation of the derivative provides a low saturated vapor pressure, lowers the sublimation temperature, and ensures the stability of its structure. It can also be used for the sublimation of indanone-C... 60 The sublimation of derivatives and the longer path of freedom provided by the plasma beam enhance the collision efficiency and product collection efficiency, while ensuring the long-term stable operation of the magnetron sputtering ion source. Furthermore, adjusting the orifice diameter effectively controls the flux and velocity angle of the plasma beam entering the reaction chamber, improving the plasma beam's effectiveness against indanone-C. 60 While improving the bombardment efficiency of derivatives, it also reduces the impact on indanone and C. 60 The derivative sublimation disrupts the flight path and improves the product yield. Attached Figure Description

[0028] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention and do not constitute a limitation thereof.

[0029] Figure 1 This is a method for preparing spin-level addressable nitrogen-intercalated indanone and C in Example 1 of the present invention. 60 A schematic diagram of a dual-cavity structure in which the ion source cavity and the reaction cavity of the derivative are connected in series;

[0030] Figure 2 This invention relates to a spin-level addressable nitrogen-intercalated indanone-C 60 A schematic diagram of the derivative and a flowchart of its preparation method;

[0031] Figure 3 The spin-level addressable nitrogen-intercalated indanone-C100 prepared in Example 1 of this invention 60 Derivatives, indanone C 60 Derivatives and C 60 Comparison of elution curves on Buckyprep column chromatography;

[0032] Figure 4 The spin-level addressable nitrogen-intercalated indanone-C100 prepared in Example 1 of this invention 60 Comparison of continuous wave electron paramagnetic resonance spectra of the derivatives in room temperature solution and solid state, where (a) is the nitrogen-intercalated indanone C 60 (a) Continuous wave electron paramagnetic resonance spectrum of the derivative in room temperature solution; (b) is the nitrogen-intercalated indanone C 60Room temperature solid-state continuous wave electron paramagnetic resonance spectrum of the derivative;

[0033] Figure 5 The spin-level addressable nitrogen-intercalated indanone-C10 packaged according to Embodiment 6 of the present invention 60 Optical photograph of the derivative;

[0034] Figure 6 The spin-level addressable nitrogen-intercalated indanone-C10 packaged according to Embodiment 6 of the present invention 60 The results of pulsed electron paramagnetic resonance (EPR) measurements of the derivatives at 5 K are shown in the figure, where (a) is the electron spin echo under magnetic field scanning; (b) is the spin-spin relaxation time measurement; (c) is the spin-lattice relaxation time measurement; and (d) is the Rabi oscillation.

[0035] Figure 7 The product prepared in Comparative Example 2 of this invention is a nitrogen-intercalated indanone with C 60 Derivatives and indanone C 60 Comparison of elution curves of derivatives on Buckyprep column chromatography. Detailed Implementation

[0036] As attached Figure 1-4 As shown, the present invention provides the following specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims. In addition, unless otherwise specified, the materials, reagents, etc., used in the following embodiments are commercially available.

[0037] The required reagents and instruments are as follows:

[0038] Indanone C 60 Derivatives (98% purity, Xiamen Funa New Materials Technology Co., Ltd.);

[0039] Toluene (HPLC grade, Thermo Fisher Scientific);

[0040] Precursor gas source (purity ≥ 99.99%, Zhuzhou Changwei Trading Co., Ltd.);

[0041] Magnetron sputtering ion implantation platform (self-built);

[0042] High-performance liquid chromatograph (Beijing Aono Technology Co., Ltd.);

[0043] Buckyprep column (20ID×250mm, Nacalai, Japan);

[0044] Continuous wave electron paramagnetic resonance spectrometer (EPR200M, QuantumCTek (Hefei) Co., Ltd.);

[0045] Pulsed electron paramagnetic resonance spectrometer (EPR100, QuantumCTek (Hefei) Co., Ltd.);

[0046] Example 1:

[0047] Figure 1 This is a method for preparing spin-level addressable nitrogen-intercalated indanone and C in Example 1. 60 A schematic diagram of a dual-cavity structure in which the ion source cavity and the reaction cavity of the derivative are connected in series;

[0048] This embodiment provides a spin-addressable nitrogen-intercalated indanone-C 60 Preparation method of derivatives. A magnetron sputtering ion implantation platform was used to prepare indanone-C... 60 Derivatives are used as sublimation raw materials, and high-purity nitrogen is used as a precursor gas source.

[0049] Magnetron sputtering ion implantation platforms include a dual-cavity structure with an ion source chamber and a reaction chamber connected in series. For example... Figure 1 As shown, in this dual-chamber structure, the reaction chamber is a cube with a length of 620 mm, a width of 520 mm, and a height of 500 mm. The ion source chamber is a cylinder with an inner diameter of 250 mm and a height of 300 mm. The circular bottom of the ion source chamber is connected to the side of the reaction chamber (the side corresponding to the width of 520 mm and the height of 500 mm), and the chambers are connected by an adjustable orifice plate (5 mm - 50 mm). The pump unit is connected to the reaction chamber but located away from the chamber containing the ion source.

[0050] The reaction chamber houses a sublimation furnace and a wound copper foil substrate. The sublimation rate of the raw materials can be controlled via PID control, while the wound copper foil prevents further damage to the deposited products from excessively long plasma beam bombardment times. Since magnetron sputtering ion sources are existing technology, they will not be described in detail here.

[0051] Figure 2 The spin-level addressable nitrogen-intercalated indanone C-type ionosphere described in the embodiment 60 A molecular schematic diagram of the derivative and a flowchart of its preparation method, which includes:

[0052] S1, 500 mg of indanone in a crucible and C 60 The derivative powder is placed in a sublimation furnace, and the substrate is positioned at the cold end of the reaction. The substrate is an 8µm copper foil substrate;

[0053] S2. A two-stage pump system consisting of a mechanical pump and a molecular pump is used to pump the gas pressure in the reaction chamber to 10. -3Pa, the orifice plate diameter is preferably 27 mm, at which point the gas pressure in the magnetron sputtering ion source cavity is 10 Pa. -2 Pa. The sublimation furnace was heated to 450°C over 45 minutes and held at that temperature for 1 hour. Simultaneously, the water cooling temperature on the back of the copper foil substrate was set to 5°C to create a larger temperature gradient and improve product collection efficiency.

[0054] S3. During the heat preservation stage, nitrogen gas at 10 sccm is introduced, and the ionization switch of the magnetron sputtering ion source is turned on. The ion source power is set to 225W to convert the nitrogen gas into a nitrogen plasma beam until the reaction is complete. This plasma beam will bombard the sublimated indanone and C in the reaction chamber. 60 Derivatives, forming nitrogen-intercalated indanone and C 60 Derivatives. The gas pressure in the magnetron sputtering ion source cavity during the reaction is 10. -1 pa, the gas pressure in the reaction chamber is 10 -2 pa;

[0055] S4. After the heat preservation stage, indanone and C are controlled by PID. 60 The sublimation rate of the derivative is The temperature is 500℃-650℃ until indanone C is obtained. 60 The derivatives were completely sublimated, and the entire process took 6 hours. During the reaction, the copper foil at the cold end of the chamber was wound up at a rate of 0.005 r / min to collect the reaction products.

[0056] S5. After the reaction is complete, the sublimation furnace is stopped from heating and allowed to cool naturally to room temperature. The pump group is then turned off to restore the gas pressure in the reaction chamber to the chamber pressure. Next, the copper foil substrate is removed and completely immersed in 1L of toluene solution. Ultrasonic treatment is used to maximize the dissolution of the product in toluene. Then, impurities insoluble in toluene are filtered out by vacuum filtration, preferably using a 0.22μm filter membrane. Finally, after drying, a spin-addressable nitrogen-intercalated indanone with C2 is obtained. 60 derivative.

[0057] Figure 3 The spin-level addressable nitrogen-intercalated indanone C-type compound prepared in Example 1 60 Derivatives, indanone C 60 Derivatives and C 60 Comparison of elution curves on a Buckyprep column, with toluene as the mobile phase and a flow rate of 12 mL / min. It can be seen that the nitrogen-intercalated indanone C... 60 Derivatives and indanone C 60 The residence times of the derivatives in the chromatographic column were basically the same, and no C was observed. 60 The corresponding peaks and other peaks indicate that indanone C 60 The derivative was not destroyed by the nitrogen plasma beam during the inlay synthesis to form C.60 Or other soluble impurities;

[0058] Figure 4 The spin-level addressable nitrogen-intercalated indanone C-type compound prepared in Example 1 60 Comparison of continuous wave electron paramagnetic resonance spectra of the derivatives in room temperature solution and solid state. Figure 4 (a) It can be seen that nitrogen-intercalated indanone and C 60 The room-temperature solution continuous-wave electron paramagnetic resonance spectrum of the derivative exhibits three signal peaks, with a peak spacing of 5.6 Guass, or 15.86 MHz, consistent with the hyperfine coupling constant of nitrogen atoms reported in the literature; simultaneously, in Figure 4 (b) Nitrogen-intercalated indanone and C 60 In addition to the three signal peaks observed in the room-temperature solid-state continuous-wave electron paramagnetic resonance spectrum of the derivative, a new signal peak also appears. This is due to the effect of indanone on C 60 The modification resulted in the breaking of the carbon cage symmetry, introducing zero-field splitting into the three-electron spin transitions in the nitrogen atom. Meanwhile, the nitrogen-intercalated indanone and C... 60 The derivative molecules are tumbling at high speeds, and the time averaging effect makes it impossible to detect zero-field splitting; therefore, nitrogen-intercalated indanone and C... 60 No signal peaks caused by zero-field splitting were observed in the continuous wave electron paramagnetic resonance spectrum of the derivative at room temperature solution.

[0059] More specifically, the above continuous-wave electron paramagnetic resonance spectrum was obtained by using 0.1 mL of a 2 mg / mL nitrogen-intercalated indanone and C... 60 A toluene solution of the derivative with 30 mg of nitrogen-intercalated indanone and C 60 The derivative solids were obtained by testing them in paramagnetic tubes with a diameter of 3 mm.

[0060] Figure 3 and Figure 4 The results collectively demonstrate the spin-level addressable nitrogen-intercalated indanone and C 60 Successful preparation of the derivative. The preparation method provided in Example 1 can collect approximately 200 mg of nitrogen-intercalated indanone and C16 derivatives. 60 The derivative, with a yield of 40% compared to the feed, contains nitrogen-intercalated indanone and C. 60 The spin content in the derivative is 120 ppm.

[0061] Example 2:

[0062] This embodiment provides a method for preparing a spin-level addressable nitrogen-intercalated indanone and C 60 The method for the derivative is the same as in Example 1, except that the diameter of the cavity orifice plate in this example is 12 mm, and the other processes are the same as in Example 1.

[0063] The preparation method provided in this embodiment can collect approximately 240 mg of nitrogen-intercalated indanone and C 60 The derivative had a yield of 48% compared to the initial feed and a spin content of 60 ppm.

[0064] In this embodiment, the increase in yield and the decrease in spin content are mainly due to the reduction in the diameter of the connecting orifice plate based on the same plasma energy. This results in a smaller divergence angle of the plasma beam velocity, but also reduces the amount of nitrogen plasma bombarding the sublimated raw material, leading to insufficient bombardment efficiency.

[0065] Example 3:

[0066] This embodiment provides a method for preparing a spin-level addressable nitrogen-intercalated indanone and C 60 The method for the derivative is the same as in Example 1, except that the diameter of the cavity orifice plate in this example is 50 mm, and the other processes are the same as in Example 1.

[0067] The preparation method provided in this embodiment can collect approximately 125 mg of nitrogen-intercalated indanone and C 60 The derivative had a yield of 25% compared to the feed and a spin content of 80 ppm.

[0068] In this embodiment, due to the increase in the diameter of the cavity orifice plate, the gas pressure in the magnetron sputtering ion source cavity during the reaction process is reduced to 10. -2 This leads to instability in the ion source power during the reaction process, and a sharp increase in the amount of plasma entering the reaction chamber. The beam cross-sectional radius expands, which further interferes with the flight angle of the sublimation material when bombarding it, resulting in a reduction in the mass of reaction products collected on the copper foil substrate.

[0069] Example 4:

[0070] This embodiment provides a method for preparing a spin-level addressable nitrogen-intercalated indanone and C 60 Compared with Example 1, the method for the derivative is the same as in Example 1, except that the gaseous precursor gas source in this example uses a mixture of 20% ammonia and 80% nitrogen, the ion source power is 450W, and the other processes are the same as in Example 1.

[0071] The preparation method provided in this embodiment can collect approximately 160 mg of nitrogen-intercalated indanone and C 60 The derivative had a yield of 32% compared to the feed and a spin content of 150 ppm.

[0072] Example 5:

[0073] This embodiment provides a method for preparing a spin-level addressable nitrogen-intercalated indanone and C 60Compared with Example 1, the method for the derivative is different in that the gaseous precursor gas source in this example uses a mixture of 20% nitric oxide and 80% nitrogen, the ion source power is 250W, and the other processes are the same as in Example 1.

[0074] The preparation method provided in this embodiment can collect approximately 195 mg of nitrogen-intercalated indanone and C 60 The derivative had a yield of 39% compared to the initial feed and a spin content of 100 ppm.

[0075] Example 6:

[0076] This embodiment focuses on spin-level addressable nitrogen-intercalated indanone and C-type... 60 The quantum properties of the derivative were tested, and the encapsulated nitrogen-intercalated indanone and C 60 Optical photographs of derivatives, such as Figure 5 As shown, the specific preparation steps are as follows:

[0077] Take 30 mg of the nitrogen-intercalated indanone C obtained in Example 1 with a spin content of 120 ppm. 60 The derivative was placed at the bottom of a paramagnetic tube with a diameter of 3 mm, compacted, and then sealed to obtain a packaged sample.

[0078] When sealing the tube, a double-row tube is needed to replace all the air in the paramagnetic tube with helium. Then, an oxyhydrogen flame is used to melt and close the end of the glass paramagnetic tube.

[0079] Figure 5 The spin-level addressable nitrogen-intercalated indanone-C-type packaged in Example 6 60 Optical photograph of the derivative;

[0080] Figure 6 The nitrogen-encapsulated indanone and C-type compound after Example 6 60 The results of pulsed electron paramagnetic resonance (PEP) testing of the derivatives at 5K are shown in the figure. The encapsulated sample was tested using a pulsed electron paramagnetic resonance spectrometer at a temperature of 5K.

[0081] Magnetic field scanning electron spin echo test: Figure 6 (a) indicates that nitrogen-intercalated indanone and C 60 The zero-field splitting parameters of the derivatives were calibrated as |D| = 17.17 MHz and E = 0.39 MHz, respectively. The zero-field splitting effect indicates that the modification with indanone disrupts the N@C splitting mechanism. 60 The isotropic nature of the S=3 / 2 spin ground state allows for addressing of individual quantum energy levels of the electron spin.

[0082] Spin-spin relaxation time and spin-lattice relaxation time measurement: Figure 6 (b) Figure 6 (c) indicates that nitrogen-intercalated indanone and C at 5K 60The derivative has a spin-spin relaxation time of 14.45 μs and a spin-lattice relaxation time of 377.87 ms.

[0083] Figure 6 (d) shows the results of the Rabi oscillation test.

[0084] The above results indicate that nitrogen-intercalated indanone and C 60 The derivatives possess excellent quantum properties and are a material with potential applications in quantum information.

[0085] Comparative Example 1:

[0086] Existing methods for preparing endohedral fullerene derivatives include two parts: the synthesis of crude endohedral fullerene products and the chemical modification of endohedral fullerenes; a spirocycloane-modified N@C was prepared. 60 Derivatives. The specific preparation steps are as follows:

[0087] S1, First is N@C 60 The synthesis of the crude product, compared to Example 1, did not use a dual-cavity structure with the ion source cavity and reaction cavity connected in series in the comparative example. Instead, the magnetron sputtering ion source was placed directly inside the reaction cavity, and the sublimation feedstock was C. 60 The sublimation rate is controlled as follows: The gaseous precursor gas source used in the reaction was high-purity nitrogen at a flow rate of 30 sccm. Other processes were the same as in Example 1. 40 mg of intrinsic N@C with a spin content of 130 ppm could be collected. 60 Compared to C 60 The yield from the initial feed was 8%.

[0088] S2, 40 mg of intrinsic N@C with a spin content of 130 ppm. 60 Mix with 40 mL of toluene and 15.6 mg of 2-bromo-1,3-indanedion (Br-IND), then slowly add 20 mL of a toluene solution of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with stirring under an argon atmosphere, and react for 1.5 h;

[0089] S3. After the reaction is complete, the preliminary purification is carried out by thin-layer chromatography with toluene:n-hexane = 1:1 as the developing solvent.

[0090] S4. The pre-purified solution was concentrated and then separated by HPLC using a 5PPB column with toluene as the mobile phase at a flow rate of 18 mL / min. The fraction with a retention time of 8.08 min was collected, dried to remove the solvent, and then dried under vacuum for 5 h to obtain approximately 15 mg of spirocycloane-modified N@C with a spin content of 112 ppm. 60 Derivatives, compared to C 60 The yield from the initial feed is 3%.

[0091] Comparative Example 2:

[0092] This comparative example provides a method for preparing nitrogen-intercalated indanone and C 60 Compared to Example 1, this comparative example did not employ a dual-cavity structure with the ion source chamber and reaction chamber connected in series; instead, the ion source was placed directly inside the reaction chamber. To ensure stable operation of the ion source, the gas flow rate was set to 30 sccm and the chamber pressure to 10 kcal / kg during the reaction. -1 pa, indanone C 60 The sublimation temperature range of the derivative is 580-720℃, and the other processes are the same as in Example 1.

[0093] The preparation method provided in this comparative example can collect approximately 50 mg of product, representing a yield of 10% compared to the initial feed, with a spin content of 53 ppm.

[0094] Figure 7 The product prepared for Comparative Example 2, indanone C 60 Derivatives and nitrogen-intercalated indanone and C 60 Comparison of elution curves of the derivatives on a Buckyprep column, with toluene as the mobile phase and a flow rate of 12 mL / min. It can be observed that the elution curve of the product prepared in Comparative Example 2 shows a significant signal between 7.7 and 9 min, indicating that in the preparation process of Comparative Example 2, indanone C... 60 The derivatives were destroyed, forming other soluble impurities.

[0095] Compared to Example 1, the impurities in the product of Comparative Example 2 were due to the low vacuum in the reaction chamber increasing the concentration of indanone and C. 60 The sublimation temperature range of the derivative leads to the formation of indanone C 60 The structure of the derivative was disrupted to some extent.

[0096] Results and Discussion:

[0097] 1. Comparison based on yield:

[0098] Comparative Example 1: 500 mg C was added. 60 Ultimately, only about 15 mg of spirocycloane-modified N@C was obtained, with a spin content of 112 ppm. 60 Derivatives, compared to C 60 The yield from the initial feed is 3%.

[0099] Comparative Example 2: 500 mg of indanone C was added. 60 The derivative can be collected to yield approximately 50 mg of product with a spin content of 53 ppm, representing a yield of 10% compared to the initial feed.

[0100] In Example 1, 500 mg of indanone C was added.60 The derivative can yield approximately 200 mg of nitrogen-intercalated indanone with a spin content of 120 ppm. 60 The derivative yield was 40% higher than that of the feedstock, thus achieving an increase in yield.

[0101] 2. Comparison based on process flow:

[0102] Compared to Comparative Example 1, the process of Example 1 does not require complex chemical modification and separation purification processes, which simplifies the experimental steps and greatly shortens the preparation time of the endohedral fullerene derivative.

[0103] 2. Currently, there are no other spin-level addressable nitrogen-intercalated indanone phenoxides with C-type spin-levels. 60 Reports on derivative preparations, in this invention using indanone-C 60 The derivative is used as a starting material to introduce zero-field splitting through indanone modification, and not all modified groups possess the structural stability in the intercalation reaction like indanone. Simultaneously, the dual-cavity structure, with the ion source cavity and reaction cavity connected in series, creates a high-vacuum environment in the reaction cavity that can provide C-terminal support for indanone. 60 The sublimation of the derivatives provides a low saturated vapor pressure, reduces the sublimation temperature range, and further ensures the stability of its structure. Figure 2 The chromatographic results also proved that indanone and C were present during the experiment. 60 The derivative exhibited good structural stability and was not destroyed by ion beams or high temperatures to become C. 60 Substances such as...

[0104] 4. Synthesized nitrogen-intercalated indanone C 60 The purpose of the derivative is to achieve spin-level addressability:

[0105] For intrinsic N@C 60 In contrast, the electronic energy levels of embedded nitrogen atoms are degenerate, requiring external modification to introduce zero-field splitting, thereby de-degenerateing the electron spin transitions and fully utilizing its energy level structure. However, intrinsic N@C... 60 Synthesis is difficult; N@C is prepared by ion implantation. 60 The crude product synthesized contains N@C 60 The content is usually one ten-thousandth, and the yield of crude product is often less than 10%. Using N@C 60 If N@C is used directly as a raw material for chemical modification, a large amount of N@C needs to be synthesized first. 60 The crude product requires purification, which is time-consuming; furthermore, the chemical modification process can also lead to the degradation of intrinsic N@C. 60 The process involves ineffective waste and the generation of byproducts, requiring further purification.

[0106] This invention uses ninhydrin C, which can be thermally sublimated. 60 Using derivatives as raw materials, spin-addressable nitrogen-intercalated indanone-C12 compounds were directly prepared. 60 The preparation steps for derivatives are simplified, and the preparation time is shortened. Nitrogen-intercalated indanone C 60 The zero-field splitting parameters of the derivatives were calibrated as |D| = 17.17 MHz and E = 0.39 MHz, respectively.

[0107] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A spin-level addressable nitrogen-intercalated indanone-C 60 The method for preparing derivatives is characterized by: Includes the following steps: S1, Add 500mg of indanone and C 60 The derivative powder raw material is placed in a crucible, and then the crucible is placed in a sublimation furnace. The substrate is placed at the cold end of the reaction, and the sublimation furnace is located inside the reaction chamber. The substrate is an 8μm copper foil substrate. The aforementioned reaction chamber is a dual-chamber structure consisting of an ion source chamber and a reaction chamber connected in series, as detailed below: The reaction chamber is a cube with a length of 620mm, a width of 520mm, and a height of 500mm; the ion source chamber is a cylinder with an inner diameter of 250mm and a height of 300mm; the circular bottom of the ion source chamber is connected to the side of the reaction chamber, and the chambers are connected by an adjustable orifice plate with a diameter of 5mm-50mm; the pump unit is connected to the reaction chamber and is located away from the chamber where the ion source is located. S2. A two-stage pump system consisting of a mechanical pump and a molecular pump is used to pump the gas pressure in the reaction chamber to 10. -3 Pa controls the sublimation furnace to heat up to 450℃ in 45 minutes and hold for 1 hour, while setting the cold end temperature to -10℃ to improve the product collection efficiency. S3. When entering the heat preservation stage, introduce a gaseous precursor gas source with a purity of ≥99.99% and a purity of 10 sccm, and turn on the ionization switch of the magnetron sputtering ion source, set the ion source power, and convert the precursor gas source into a nitrogen-containing low-temperature plasma beam until the reaction ends. S4. After the heat preservation stage, indanone and C are controlled by PID. 60 The sublimation rate of the derivative is The temperature is 500℃-650℃ until the indanone C in the crucible is obtained. 60 The derivatives were completely sublimated, and the entire process was controlled within 6 hours. During the reaction, the copper foil at the cold end of the reaction chamber was wound up at a rate of 0.005 r / min to collect the reaction products. S5. After the reaction is complete, the sublimation furnace is stopped from heating and allowed to cool naturally to room temperature. The pump group is then turned off to restore the gas pressure in the reaction chamber to the normal pressure. The copper foil substrate is then removed and placed in a toluene solution. After sonication, filtration, and drying, a spin-addressable nitrogen-intercalated indanone and C2 are obtained. 60 derivative.

2. A spin-level addressable nitrogen-intercalated indanone-C10 according to claim 1 60 The method for preparing derivatives is characterized by: The spin-level addressable nitrogen-intercalated indanone and C described in S1 60 The derivatives are stable at high temperatures, and their structure is not destroyed during the reaction.

3. A spin-level addressable nitrogen-intercalated indanone-C10 according to claim 1 60 The method for preparing derivatives is characterized by: The tandem dual-chamber structure described in S1 creates a pressure gradient distribution during the reaction process. After introducing a 10 sccm gaseous precursor gas source, the pressure in the reaction chamber becomes 10. -2 The gas pressure in the magnetron sputtering ion source cavity is 10 Pa. -1 pa.

4. A spin-level addressable nitrogen-intercalated indanone-C10 according to claim 1 60 The method for preparing derivatives is characterized by: The gaseous precursor gas source mentioned in S3 is nitrogen or ammonia, or a mixture of nitrogen, nitric oxide, nitrogen dioxide, and ammonia; the low-temperature plasma beam bombards the sublimated indanone and C in the reaction chamber. 60 Derivatives, forming spin-addressable nitrogen-intercalated indanone and C 60 derivative.

5. A spin-addressable nitrogen-intercalated indanone-C 60 The derivative is characterized by: A spin-level addressable nitrogen-intercalated indanone C according to any one of claims 1-4 60 The method for preparing the derivative was obtained, and N@C was achieved through modification with indanone. 60 The symmetry breaking leads to zero-field splitting, which degenerates the electron spin transitions of the embedded nitrogen atoms and gives them good spin level addressability. The zero-field splitting parameters are calibrated as |D| = 17.17 MHz and E = 0.39 MHz, respectively.

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